Acid wool dyestuffs of the anthraquinone series



" ble addition tokn'owndyestu s5 ing constitution:

Patented Feb; 6, 1940 {STATES A0115 wooL DYES'IYUFFS OF THE ANTHRAQUINONE-YISERIES Hans Schlichenmeier, Frankfort-on-theeMain- Hochst, Germany, assignor. to (ieneral Aniline & Film Corporation, a corporation of Delaware NDDIQ'W Dg plic tion uly 3, 1937', Serial No.

n 151,965. InGermanyJuly 9, 1936 ownie (e u--312) The present invention relatestc acid wool dyestufis of the anthr'aquinoneseriesi I have found that new blueto violet acid wooldyestufis of the anthraquinone series are obtained by treating withal halogenating agent,

advantageously in the presence of a halogenae tion catalyst, such as iodine or iron, a dyestuff of the general formula:

' a? SOsX wherein X is hydrogen or an: alkali metal atom and Y stands for an aryl*group,"for instance, of the benzene series. 1 The halogenation may be performed, for instance, in an aqueous suspension or in a sulfuric acid solution. By applying predetermined quantities ot-thehalogen, monoor di-halogen compounds may be obtained without incurring the elimination of the sulfo group. By

the introduction oi thewhalogen the shade of the new dyestuffs is displaced to the red side in com parison with the parent-dyestuffs, this the more so the more halogen has been introduced. Due to the beautiful shade and theirrgcod properties of fastness the new'dyestuffs constitute a valuafhei llm neeaemh e e invehti'ohi-butthey'are notintended to limit it "thereto; the parts are by weight, unless other wise stated: I

'(1) 24 parts of .thedyestufi having thefollow- SOaNu NHcobHe are introducedat 0 G. into 250 parts by volume of sulfuric acid of 66 B.

to illustrate the 1 As soon as thedyestuff has dissolved, 0.5 part of iodine is added and gaseous chlorine is introduced at 0 C.to 10? -'C., until after escape of the hydrogen chloride formed: the weight of the mixture hasincreased The mixture is then poured v by about two parts. Onice, filteredriwith suction and. the solid'matter;

washeduntil neutral and dried, The, new; dye-- stuff thus} obtained is a crystal ine blue powder;

It;contains; one atom in proportion; of chlorine; I 'It; dyes, wool in an acid bath fast blue tints which aremuch redder than thoseobtained with the (2)24 partsio ftheparent material oi} Exam-vle re dis olvedat o C- n 30 ;na1ts:-.

byvolume of sulfuricacidof- 6.6- B. After ad:

dition, of 0.5 part of" iodine, at about ifi; C., 9

parts of bromineare added drop trum Eye drogenbromide is evolved. Inorder to complete the reactionline whole is stirred overnight at room; temperature and; then pouredupon-ice; a ue dy s ufl Wh chc asseoarat d s filt r d with suction and washed with water until neutral; When dry, it is a blue powder which dyes W fast-bl nt Theldy stuff. ontains; on atom in proportion of bromine 3) 24 parts of the parent material oi Exam ple 1 are dissolved in 300 parts byvolu-Ineof sulfuric acid of 66 B. After addition of 05 part i of iodine 18 parts of bromine are added drop by drop at room ten iperature. The bromine is caused to react for/5 0 hours at room. temperature,

a large amount of hydrogen bromide being evolved. The'dyestuff obtained is workedup as usual. In the dry statait is a blue powder corttainingZ atomic proportions of bromine. 1

; (4) 25fparts of the dyestuif of the following constitution: I

' SOaNa N- CHS I CQ.CH3

- are converted into the mono-halogen compounds,

as described in Examples 1 and 2. The new dyestufi's dye wool tints which are distinctly redder than those of the parent dyestuff. The dyeing's possess good properties of fastness;

(5) By causing 2 molecular proportions of bro? mine to act as described in Example 3 upon the dyestufi used as parent material in Example 4, a dyestuff is obtained which dyes wool violet tints of good properties of fastness.

(6) 20 parts of sodium l-amino-l-anilino-anthraquinone-2-sulfonate are dissolved in 400 parts of sulfuric acid of 30%. After addition of 0.5 gram of iodine, 8 parts of bromine are added, drop by drop, at 0 C. to 5 C. The whole is further stirred for 2 /2 hours, and then is poured upon ice and the blue precipitate obtained is filtered with suction. The product is then washed with a sodium chloride solutionuntil neutral and dried. The new dyestufi is a blue powder which dissolves in concentrated sulfuric acid to a green-blue solution, It contains one atomic proportion of bromine.

('7) 10 parts of 1-amin0-4-anilino-anthraquinone-Z-sulfonic acid are made into a suspension with 200 parts of water. After additionof 0.25 part of iodine, 4 parts of bromine in 25 parts of concentrated hydrochloric acid are added, drop by drop. The mixture is heated, while stirring, for about 30 hours at 25 C. to 30 C. and the dyestuif formed is filtered with suction. It contains one atomic proportion of bromine. The bromine atom stands, however, apparently in another position than in the dyestufl obtained according to the process of Example 6.

(8) 20 parts of 1-amino-4-anilino-anthraquinone-2-sulfonic acid are dissolved in 300 parts of sulfuric acid of 66 B. and 8 parts of bromine are added drop by drop at about 0 C. The whole is further stirred for about 5 hours, the dyestuff solution containing the sulfuric acid is poured upon ice and the blue dyestuif thus obtained is filtered with suction. When dry, it is a blue powder having similar dyeing properties as the dyestufi obtained according to the process of Example 6.

I claim: 1. The compounds of the general formula:

(N) NE:

SOaONa /X NH- -N wherein X represents a member of the group consisting of hydrogen and methyl, Y represents a member of the group consisting of C1, C12, Br and Brz, being dyestuffs of good fastness properties.

2. The compound of the formula:

being a blue powder which dyes wool fast blue tints.

3. The compound of the formula:

/SO1ON:\

o r m Nnooom being a blue powder.

4. The compound of the formula:

N-CHI being a dyestufi which dyes wool violet tints of good properties of fastness.

HANS SCI-ILICHENMEIER. 

